Full-Scale Remediation of a Jet Fuel-Contaminated Soil: Assessment of Biodegradation, Volatilization, and Bioavailability

Here, we addressed biodegradation vs. volatilization processes, and also bioavailability limitations during biopile remediation of soil initially contaminated by more than 5,000 mg/kg of hydrocarbons. In order to select bioremediation strategies, we first conducted a biotreatability study, which included geochemical, textural, and microbiological characterization of the soil matrix. Next, we implemented five bioremediation approaches onsite in real-scale biopiles. In order to monitor hydrocarbon depletion and to distinguish between biological and non-biological processes, we analyzed chemical biomarkers by means of gas chromatography?Cmass spectrometry. In addition, a comprehensive study of soil grain size and its implications on bioavailability were studied. Furthermore, the evolution of microbial populations was also examined. Two of the strategies implemented in the biopiles (the combination of a slow-release fertilizer and a surfactant, and the use of an oleophilic fertilizer respectively) reduced the soil hydrocarbon content to under 500 mg/kg in 5 months. Additional results from this study indicate that volatilization was the predominant degradation process for light hydrocarbons (below 12 carbon atoms), whereas heavier compounds were mainly biodegraded. However, even in the most favorable situation, a residual concentration of hydrocarbons linked to the finer fraction of the soil was found.     

Quality and aromatic sensory descriptors (mainly fresh and dry fruit character) of Spanish red wines can be predicted from their aroma-active chemical composition

A satisfactory model explaining quality could be built in a set of 25 high quality Spanish red wines, by aroma-active chemical composition. The quality of the wines was positively correlated with the wine content in fruity esters, acids, enolones, and wood derived compounds, and negatively with phenylacetaldehyde, acetic acid, methional, and 4-ethylphenol. Wine fruitiness was demonstrated to be positively related not only to the wine content on fruity esters and enolones, but to wine volatile fatty acids. Fruitiness is strongly suppressed by 4-ethylphenol, acetic acid, phenylacetaldehyde, and methional, this involved in the perception of dry-fruit notes. Sensory effects were more intense in the presence of β-damascenone and β-ionone. A satisfactory model explaining animal notes could be built. Finally, the vegetal character of this set of wines could be related to the combined effect of dimethylsulfide (DMS), 1-hexanol, and methanethiol.     

Genetic characterization of a collection of chayote, <Emphasis Type="Italic">Sechium edule</Emphasis> (Jacq.) Swartz,in Costa Rica by using isozyme markers

We established protocols for the analysis of genetic diversity in chayote (Sechium edule) by using isozyme markers, thereby determining the level of genetic diversity present in 42 accessions of chayote from Costa Rica. We obtained clear and reproducible zymograms for eight enzyme staining systems: PGM, 6-PGD, PGI, IDH, MDH, SOD, SKD, and EST, and were able to score 14 putative loci. Eight of the 14 loci examined were polymorphic. We found 35 distinct multilocus genotypes among these accessions. Five of these multilocus genotypes were homozygous for all loci. In addition, our data also revealed that most of the multilocus genotypes (24) were heterozygous for only one of the eight loci, and the rest were heterozygous for two or three loci (9 and 4 accessions, respectively). Seven multilocus genotypes were found in two different accessions. Dice similarity coefficient was used to study the relationship between accessions. This analysis, based on the presence and absence of alleles, revealed that accessions collected in the same location seldom shared the same multilocus genotype. The value of isozyme polymorphisms as tools to continue studies on the characterization of chayote is discussed.     

Chemical characterization of lignin and lipid fractions in industrial hemp bast fibers used for manufacturing high-quality paper pulps

The chemical composition of lignin and lipids of bast fibers from industrial hemp (Cannabis sativa) used for high-quality paper pulp production was studied. Pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) of fibers showed a lignin with a p-hydroxyphenyl:guaiacyl:syringyl unit (H:G:S) molar proportion of 13:53:34 (S/G ratio of 0.64). p-Hydroxycinnamic acids, namely, p-coumaric and ferulic acids, were found in only trace amounts. Among the lipids, the main compounds identified by GC/MS of the hemp fibers extracts were series of n-alkanes, free and esterified sterols and triterpenols, waxes, and long-chain n-fatty acids. Other compounds such as n-aldehydes, n-fatty alcohols, steroid hydrocarbons, and steroid and triterpenoid ketones as well as steryl glycosides were also found.     

Cytogenetic variation in somatic tissue cultures and regenerated plants of barley (Hordeum vulgare L.)

Summary Chromosome number of morphogenic and non-morphogenic calli and regenerated plants of barley were determined. Cultures were obtained from two kinds of explants, immature embryos and seedling leaves from three cultivars, Ingrid, Dissa and Golden Promise. Callus chromosome analyses were carried out during a 12 month period in a medium containing 2 mg/l of 2,4-D. Diploid cells were predominant in all cases; although in leaf-derived cultures, retraploid cells (2n=4x=28) showed a tendency to increase as time in culture increased and after more than six months in culture, diploid cells decreased to percentages of almost 70%. Aneuploid cells were generally infrequent in all cases. The source of explant has been more important than the genotype (cultivar) and the type of callus (morphogenic vs. non-morphogenic) in the chromosomal stability of cultures as time increases. From short term cultures, only 1.85% of the regenerated plants were tetraploid, the remaining were diploids. The ability of morphogenic calli to regenerate plants decreased before any significant reduction of diploid cells were observed.     

Time-resolved spectral studies of blue-green fluorescence of artichoke (Cynara cardunculus L. Var. Scolymus) leaves: identification of chlorogenic acid as one of the major fluorophores and age-mediated changes

Synchrotron radiation and the time-correlated single-photon counting technique were used to investigate the spectral and time-resolved characteristics of blue-green fluorescence (BGF) of artichoke leaves. Leaves emitted BGF under ultraviolet (UV) excitation; the abaxial side was much more fluorescent than the adaxial side, and in both cases, the youngest leaves were much more fluorescent than the oldest ones. The BGF of artichoke leaves was dominated by the presence of hydroxycinnamic acids. A decrease in the percentage of BGF attributable to the very short kinetic component (from 42 to 20%), in the shape of the BGF excitation spectra, and chlorogenic acid concentrations indicate that there is a loss of hydroxycinnamic acid with leaf age. Studies on excitation, emission, and synchronized fluorescence spectra of leaves and trichomes and chlorogenic acid contents indicate that chlorogenic acid is one of the main blue-green fluorophores in artichoke leaves. Results of the present study indicate that 20-42% (i.e., the very short kinetic component) of the overall BGF is emitted by chlorogenic acid. Time-resolved BGF measurements could be a means to extract information on chlorogenic acid fluorescence from the overall leaf BGF.     

Bradford-reactive soil proteins and aggregate stability under abandoned versus tilled olive groves in a semi-arid calcisol

Glomalin, a substance produced by arbuscular mycorrhizal fungi, is reported to play a role in soil aggregation, but this role has been questioned in soils rich in calcium carbonate. We studied the relationship between aggregation stability and glomalin in a Haplic Calcisol comparing abandoned and active cultivation of olive groves. Abandonment was associated with increases in soil organic carbon, the percentage of water stable aggregates (WSA_1-2mm), and easily extractable and total Bradford-reactive soil protein. WSA_1-2mm was strongly positively correlated with both easily extractable and total Bradford-reactive soil protein. While easily extractable Bradford-reactive soil protein measured in both stable and unstable aggregates did not show any significant differences, Bradford-reactive soil protein was twice as high in stable than in unstable aggregates under both tillage and abandonment. Our results suggest that Bradford-reactive soil protein influences aggregate stability, even in soils with low organic matter and high calcium carbonate contents. However, more research is needed to elucidate the role of easily extractable Bradford-reactive soil protein in soil aggregation.     

Degradation by Solar Radiation of Estrogenic Hormones Monitored by UV?CVisible Spectroscopy and Capillary Electrophoresis

This work aims to study the degradation of estrone, 17??-estradiol, 17??-ethinylestradiol, and estriol under direct solar radiation, with an average irradiance value of 5.2?kWh/m². Degradation at different temperatures (4??C, 20??C, and 30??C) was also tested in darkness. Individual solutions of the four estrogens were prepared and subjected to the conditions referred to above. The degradation for each compound was followed, after 7, 14, 21, 28, 35, 63, 91, and 126?days measuring the absorbance at the wavelength of 281?nm. The degradation of the four mixed estrogens was determined using capillary electrophoresis (CE), with a diode array detector and cholic acid, sodium salt plus sodium borate as a background buffer. The results showed no significant degradation rates on samples subjected to different temperatures. However, the results from CE analysis showed that, under direct solar radiation, after 126?days, the degradation rate varied between 75% and 100%. Also, the UV?CVis showed significant changes in the shape of UV?CVis spectra under direct solar radiation.     

Characterization of sulfated quercetin and epicatechin metabolites

Different monosulfates of quercetin and epicatechin with metabolic interest were obtained by hemisynthesis and characterized regarding their chromatographic behavior and absorption and mass spectra. Three of these compounds were further isolated, and their structures were elucidated by mass spectrometry and (1)H and (13)C nuclear magnetic resonance using one- and two-dimensional techniques (heteronuclear single-quantum coherence and heteronuclear multiple-bond correlation). The calculation of the proton and carbon shifts caused by sulfation allowed for the assignment of the position of the sulfate group in the flavonoids, so that the compounds were identified as quercetin-3'-O-sulfate, quercetin 4'-O-sulfate, and epicatechin 4'-O-sulfate. It was found that sulfation at position 3' induced a large upfield shift in the carbon bearing the sulfate group and downfield displacements of the adjacent carbons, whereas no significant upfield or downfield shifts were observed with respect to the parent flavonoid when sulfation was produced at position 4'.     

High-resolution NMR and diffusion-ordered spectroscopy of port wine

The use of high-resolution NMR and high-resolution diffusion-ordered spectroscopy (DOSY) for the characterization of selected Port wine samples of different ages with the aim of identifying changes in composition is described. Conventional 1D and 2D NMR methods enabled the identification of about 35 compounds, including minor components such as some medium-chain alcohols, amino acids, and organic acids. High-resolution (HR) DOSY extended sample characterization, increasing the number of compounds identified and NMR assignments made, by providing information on the relative molecular sizes of the metabolites present. Port wines of different ages were found to differ mainly in their content of (a) organic acids and some amino acids, (b) an unidentified possible disaccharide, and (c) large aromatic species. The relative amount of these last high Mw aromatics is seen to decrease significantly in the oldest wine, as expected from the known formation and precipitation of anthocyanin-based polymers during red wine aging.